References

ACPD

Atmospheric Chemistry and Physics Discussions

ACPD

1680-7375

Copernicus GmbH

Göttingen, Germany

10.5194/acpd-11-28273-2011

Modelling the partitioning of ammonium nitrate in the convective boundary layer

Aan de Brugh

J. M. J.

¹ ² Henzing

J. S.

² Schaap

² Morgan

W. T.

³ Coe

³ Krol

M. C.

¹ ⁴

Meteorology and Air Quality Section, Wageningen University, Wageningen, The Netherlands

TNO, Earth, Environment and Life Sciences, Research Group Climate, Air and Sustainability, Utrecht, The Netherlands

Centre for Atmospheric Science, University of Manchester, Manchester, UK

Institute for Marine and Atmospheric Research Utrecht, The Netherlands

20 10 2011

11 10 28273 28317

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An explanatory model study is presented on semi-volatile secondary inorganic aerosols on three clear days in May 2008 during the IMPACT campaign at the Cabauw tower in the Netherlands. A single column model in combination with the equilibrium aerosol model ISORROPIA is used. This model uses surface observations from IMPACT and calculates the gas-aerosol partitioning of ammonium nitrate. The calculated gas-aerosol equilibrium overestimates the gas phase fraction during daytime, and overestimates the aerosol phase fraction during night-time. This discrepancy can partly be solved when the approach of the gas-aerosol equilibrium is forced to proceed with a delay timescale of up to two hours. Although it is shown that the delay itself has a small effect, the most important effect is caused by the mixing of air from higher altitudes at which the equilibrium is shifted to the aerosol phase. Thus, vertical mixing is shown to have a significant influence on the calculated partitioning at the surface. In some occasions, the correspondence to the observed partitioning improves dramatically. Even though gas-aerosol partitioning of ammonium nitrate is not instantaneous, observations show that a different equilibrium in the upper boundary layer causes aerosol ammonium nitrate concentrations to increase with altitude. Our model calculates similar vertical gradients depending on the assumed speed of gas-aerosol equilibrium. The calculated optical properties of the aerosol show a similar behaviour. The aerosol optical properties depend on the aerosol size distribution both directly, because light scattering depends on particle size, and indirectly, because the equilibration timescale depends on the aerosol sizes. Future studies should therefore focus on a fully size-resolved treatment of the gas-aerosol partitioning. Finally, coarser-resolution models may treat the gas-aerosol equilibrium of ammonium nitrate by calculating the equilibrium with a temperature and humidity sampled at a different altitude. We found that the equilibrium at an altitude of 200 m (night) up to 600 m (day) is representative for the partitioning of ammonium nitrate at the surface in the beginning of May 2008.

References 1

Anderson, T L., Covert, D S., Marshall, S F., Laucks, M L., Charlson, R J., Waggoner, A P., Ogren, J A., Caldow, R., Holm, R L., Quant, F R., Sem, G J., Wiedensohler, A., Ahlquist, N A., and Bates, T S.: Performance characteristics of a high-sensitivity, three-wavelength, total scatter/backscatter nephelometer, J. Atmos. Ocean. Tech., 13, 967–986, http://dx.doi.org/10.1175/1520-0426(1996)013<0967:PCOAHS>2.0;2doi:10.1175/1520-0426(1996)013<0967:PCOAHS>2.0;2, 1996.

Aspnes, D E., Theeten, J B., and Hottier, F.: Investigation of effective-medium models of microscopic surface roughness by spectroscopic ellipsometry, Phys. Rev. B., 20, 3292–3302, http://dx.doi.org/10.1103/PhysRevB.20.3292doi:10.1103/PhysRevB.20.3292, 1979.

Bruggeman, D. A G.: Berechnung verscheidener physikalischer Konstanten von heterogenen Substanzen, 1 Dielektrizitätskonstanten und Leitfähigkeiten der Mischkörper aus isotropen Substanzen, Ann. Phys., 416, 636–664, http://dx.doi.org/10.1002/andp.19354160802doi:10.1002/andp.19354160802, 1935.

Canagaratna, M R., Jayne, J T., Jimenez, J L., Allan, J D., Alfarra, M R., Zhang, Q., Qnasch, T B., Drewnick, F., Coe, H., Middlebrook, A., Delia, A E., Williams, L R., Trimborn, A M., Northway, M J., DeCarlo, P .F., Kolb, C E., Devidovits, P., and Worsnop, D R.: Chemical and microphysical characterization of ambient aerosols with the aerodyne aerosol mass spectrometer, Mass Spectrom. Rev., 26, 185–222, http://dx.doi.org/10.1002/mas.20115doi:10.1002/mas.20115, 2007.

Capaldo, K P., Pilinis C., and Pandis, S N.: A computationally efficient hybrid approach for dynamic gas/aerosol transfer in air quality models, Atmos. Environ., 34, 3617–3627, http://dx.doi.org/10.1016/S1352-2310(00)00092-3doi:10.1016/S1352-2310(00)00092-3, 2000.

Cheng, Y H. and Tsai, C J.: Evaporation loss of ammonium nitrate particles during filter sampling, J. Aerosol Sci., 28, 1553–1567, http://dx.doi.org/10.1016/S0021-8502(97)00033-5doi:10.1016/S0021-8502(97)00033-5, 1997.

DeCarlo, P F., Slowik, J G., Worsnop, D R., Davidovits, P., and Jimenez, J L.:Particle morphology and density characterization by combined mobility and aerodynamic diameter measurements. Part 1: Theory, Aerosol Sci. Technol., 38, 1185–1205, http://dx.doi.org/10.1080/027868290903907doi:10.1080/027868290903907, 2004.

Drewnick, F., Hings, S S., DeCarlo, P F., Jayne, J T., Gonin, M., Fuhrer, K., Weimer, S., Jimenez, J L., Demerjian, K L., Borrmann, S., Worsnop, and D R.: A new time-of-flight aerosol mass spectrometer (TOF-AMS) – Instrument description and first field deployment, Aerosol Sci. Technol., 39, 637–658, http://dx.doi.org/10.1080/02786820500182040doi:10.1080/02786820500182040, 2005.

Feng, Y. and Penner, J E.: Global modeling of nitrate and ammonium: Interaction of aerosols and tropospheric chemistry, J. Geophys. Res., 112, D01304, http://dx.doi.org/10.1029/2005JD006404doi:10.1029/2005JD006404, 2007.

Fisseha, R., Dommen, J., Gutzwiller, L., Weingartner, E., Gysel, M., Emmenegger, C., Kalberer, M., and Baltensperger, U.: Seasonal and diurnal characteristics of water soluble inorganic compounds in the gas and aerosol phase in the Zurich area, Atmos. Chem. Phys., 6, 1895–1904, http://dx.doi.org/10.5194/acp-6-1895-2006doi:10.5194/acp-6-1895-2006, 2006.

Fountoukis, C. and Nenes, A.: ISORROPIA II: a computationally efficient thermodynamic equilibrium model for K$^+$–Ca$^2+$–Mg$^2+$–NH$_4^+$–Na$^+$–SO$_4^2-$–NO$_3^-$–Cl$^-$–H2O aerosols, Atmos. Chem. Phys., 7, 4639–4659, http://dx.doi.org/10.5194/acp-7-4639-2007doi:10.5194/acp-7-4639-2007, 2007.

Haywood, J. and Boucher, O.: Estimates of the direct and indirect radiative forcings due to tropospheric aerosols: a review, Rev. Geophys., 38, 513–543, http://dx.doi.org/10.1029/1999RG000078doi:10.1029/1999RG000078, 2000.

Hecht, E.: Optics, Fourth edition, Addison-Wesley Publishing Co., Reading, Pennsylvania, 2003.

Hess, M., Koepke, P., and Schult, I.: Optical Properties of Aerosols and Clouds: The Software Package OPAC, B. Am. Meteorol. Soc., 79, 831–844, http://dx.doi.org/10.1175/1520-0477(1998)079<0831:OPOAAC>2.0.CO;2doi:10.1175/1520-0477(1998)079<0831:OPOAAC>2.0.CO;2, 1998.

Hong, S.-Y. and Pan, H.-L.: Nonlocal boundary layer vertical diffusion in a Medium-Range Forecast model, Mon. Weather Rev., 124, 2322–2339, http://dx.doi.org/10.11751520-0493(1996)124<2322:NBLVDI>2.0.CO;2doi:10.11751520-0493(1996)124<2322:NBLVDI>2.0.CO;2, 1996.

Intergovernmental Panel on Climate Change, edited by: Solomon, S., Qin, D., Manning, M., Chen, Z., Marquis, M., Averyt, K B., Tignor, M., and Miller, H L.: Climate change 2007: The physical Science Basis, IPCC Fourth Assassement report (AR4), 2007.

Jarvis, P G.: The interpretation of the variations in leaf water potentials and stomatal conductance found in canopies in the field, Philos. Trans. R. Soc. Lond. B273, 593–610, http://dx.doi.org/10.1098/rstb.1976.0035doi:10.1098/rstb.1976.0035, 1976.

Kaufman, Y J., Tenré, D., and Boucher, O.: A satellite view of aerosols in the climate system, Nature, 419, 215–223, http://dx.doi.org/10.1038/nature01091doi:10.1038/nature01091, 2002.

Keuken, M P., Schoonebeek, C A M., Vanwensveenlouter, A., and Slanina, J.: Simultaneous Sampling of NH3, HNO3, HCl, SO2 and H2O2 in Ambient Air by a Wet Annular Denuder System, Atmos. Environ., 22, 2541–2548, http://dx.doi.org/10.1016/0004-6981(88)90486-6doi:10.1016/0004-6981(88)90486-6, 1988.

Khlystov, A., Wyers, G P., and Slanina, J.: The Steam-Jet Aerosol Collector, Atmos. Environ., 29, 2229–2234, http://dx.doi.org/10.1016/1352-2310(95)00180-7doi:10.1016/1352-2310(95)00180-7, 1995.

Kulmala, M., Asmi, A., Lappalainen, H. K., Carslaw, K. S., Pöschl, U., Baltensperger, U., Hov, Ø., Brenquier, J.-L., Pandis, S. N., Facchini, M. C., Hansson, H.-C., Wiedensohler, A., and O'Dowd, C. D.: Introduction: European Integrated Project on Aerosol Cloud Climate and Air Quality interactions (EUCAARI) – integrating aerosol research from nano to global scales, Atmos. Chem. Phys., 9, 2825–2841, http://dx.doi.org/10.5194/acp-9-2825-2009doi:10.5194/acp-9-2825-2009, 2009.

Madronich, S.: Photodissociation in the atmosphere. 1. Actinic flux and the effect of ground reflections and clouds, J. Geophys. Res., 92, 9740–9752, http://dx.doi.org/10.1029/JD092iD08p09740doi:10.1029/JD092iD08p09740, 1987.

Metzger, S., Dentener, F., Krol, M., Jeuken, A., and Lelieveld, J.: Gas/aerosol partitioning~2: Global modeling results, J. Geophys. Res., 107, 4313, http://dx.doi.org/10.1029/2001JD001103doi:10.1029/2001JD001103, 2002a.

Metzger, S., Dentener, F., Pandis, S., and Lelieveld, J.: Gas/aerosol partitioning~1: A computationally efficient model, J. Geophys. Res., 107, 4312, http://dx.doi.org/10.1029/2001JD001102doi:10.1029/2001JD001102, 2002b.

Meng, Z. and Seinfeld, J H.: Time scales to achieve atmospheric gas-aerosol equilibrium for volatile species, Atmos. Environ., 30, 2889–2900, http://dx.doi.org/10.1016/1352-2310(95)00493-9doi:10.1016/1352-2310(95)00493-9, 1996.

Morgan, W T., Allan, J D., Bower, K N., Esselborn, M., Harris, B., Henzing, J S., Highwood, E J., Kiendler-Scharr, A., McMeeking, G R., Mensah, A A., Northway, M J., Osborne, S., Williams, P I., Krejci, R., and Coe, H.: Enhancement of the aerosol direct radiative effect by semi-volatile aerosol components: airborne measurements in North-Western Europe, Atmos. Chem. Phys., 10, 8151–8171, http://dx.doi.org/10.5194/acp-10-8151-2010doi:10.5194/acp-10-8151-2010, 2010.

Morino, Y., Kondo, Y., Takegawa, N., Miyazaki, Y., Kita, K., Komazaki, Y., Fukuda, M., Miyakawa, T., Moteki, N., and Worsnop, D R.: Partitioning of HNO3 and particulate nitrate over Tokyo: Effect of vertical mixing, J. Geophys. Res., 111, D15215, http://dx.doi.org/10.1029/2005JD006887doi:10.1029/2005JD006887, 2006.

Moya, M., Ansari, A S., and Pandis, S N.: Partitioning of nitrate and ammonium between the gas and particulate phases during the 1997 IMADA-AVER study in Mexico City, Atmos. Environ., 35, 1791–1804, http://dx.doi.org/10.1016/S1352-2310(00)00292-2doi:10.1016/S1352-2310(00)00292-2, 2001.

Nenes, A., Pandis, S N., and Pilinis, C.: ISORROPIA: A new thermodynamic equilibrium model for multiphase multicomponent inorganic aerosols, Aquat. Geochem., 4, 123–152, http://dx.doi.org/10.1023/A:1009604003981doi:10.1023/A:1009604003981, 1998.

Noh, Y., Chun, W G., Hong, Y., and Raasch, S.: Improvement of the K-profile model for the planetary boundary layer based on large eddy simulation data, Bound. Lay. Meteorol., 107, 401–427, http://dx.doi.org/10.1023/A:1022146015946doi:10.1023/A:1022146015946, 2003.

Putaud, J.-P., Raes, F., van Dingenen, R., Brüggemann, E., Facchini, M C., Decesari, S., Fuzzi, S., Gehrig, R., Hüglin, C., Laj, P., Lorbeer, G., Maenhaut, W., Mihalopoulos, N., Müller, K., Querol, X., Rodriguez, S., Schneider, J., Spindler, G., ten Brink, H., T\o rsetb, K., and Wiedensohler, A.: A European aerosols phenomenology–2: chemical characteristics of particulate matter at kerbside, urban, rural and background sites in Europe, Atmos., Environ., 38, 2579–2595, http://dx.doi.org/10.1016/j.atmosenv.2004.01.041doi:10.1016/j.atmosenv.2004.01.041, 2004.

Rosenfeld, D., Lohmann, U., Raga, G B., O'Dowd, C D., Kulmala, M., Fuzzi, S., Reissell, A., and Andreae, M O.: Flood or Drought: How Do Aerosols Affect Precipitation?, Science, 321, 1309–1313, http://dx.doi.org/10.1126/science.1160606doi:10.1126/science.1160606, 2008.

Russchenberg, H W J., Bosveld, F., Swart, D., ten Brink, H., de Leeuw, G., Uijlenhoet, R., Arbesser-Rastburg, B., van der Marel, H., Ligthart, L., Boers, R., and Apituley, A.: Ground-based atmospheric remote sensing in The Netherlands; European outlook, IEICE Transactions on Communications E88-B(6), 2252–2258, http://dx.doi.org/10.1093/ietcom/e88-b.6.2252doi:10.1093/ietcom/e88-b.6.2252, 2005.

Schaap, M., Müller, K., and ten Brink, H. M.: Constructing the European aerosol nitrate concentration Field from quality analysis data, Atmos. Environ., 36, 1323–1335, http://dx.doi.org/10.1016/S1352-2310(01)00556-8doi:10.1016/S1352-2310(01)00556-8, 2002.

Schaap, M., van Loon, M., ten Brnik, H M., Dentener, F J., and Builtjes, P J H.: Secondary inorganic aerosol simulations for Europe with special attention to nitrate, Atmos. Chem. Phys., 4, 857–874, http://dx.doi.org/10.5194/acp-4-857-2004doi:10.5194/acp-4-857-2004, 2004.

Schaap, M., Otjes, R P., and Weijers, E P.: Illustrating the benefit of using hourly monitoring data on secondary inorganic aerosol and its precursors for model evaluation, Atmos. Chem. Phys. Discuss., 10, 12341–12370, http://dx.doi.org/10.5194/acpd-10-12341-2010doi:10.5194/acpd-10-12341-2010, 2010.

Steeneveld, G J., van de Wiel, B J H., and Holtslag, A A M.: Diagnostic equations for the stable boundary layer height: Evaluation and dimensional analysis, J. Appl. Meteorol. Clim., 46, 212–225, http://dx.doi.org/10.1175/JAM2454.1doi:10.1175/JAM2454.1, 2007.

Takahama, S., Wittig, A E., Vayenas, D V., Davidson, C I., and Pandis, S M.: Modeling the diurnal variation of nitrate during the Pittsburgh Air Quality Study, J. Geophys. Res., 109, D16S06, http://dx.doi.org/10.1029/2003JD004149doi:10.1029/2003JD004149, 2004.

Tang, I N.: Chemical and size effects of hygroscopic aerosols on light scattering coefficients, J. Geophys. Res., 101, 19245–19250, http://dx.doi.org/10.1029/96JD03003doi:10.1029/96JD03003, 1996.

ten Brink, H M., Plomp, A., Spoelstra, H., and van de Vate, J F.: A high-resolution electrical mobility aerosol spectrometer (MAS), J. Aerosol Sci., 14, 589–597, http://dx.doi.org/10.1016/0021-8502(83)90064-2doi:10.1016/0021-8502(83)90064-2, 1983.

ten Brink, H M., Kruisz, C., Kos, G P A., and Berner, A.: Composition/size of the light-scattering aerosol in the Netherlands, Atmos. Environ., 31, 3955–3962, http://dx.doi.org/10.1016/S1352-2310(97)00232-Xdoi:10.1016/S1352-2310(97)00232-X, 1997.

ten Brink, H., Otjes, R., Jongeman, P., and Kos, G.: Monitoring of the ratio of nitrate to sulphate in size-segregated submicron aerosol in the Netherlands, Atmos. Res., 92, 270–276, http://dx.doi.org/10.1016/j.atmosres.2008.12.003doi:10.1016/j.atmosres.2008.12.003, 2009.

Thomas, R M., Trebs, I., Otjes, R., Jongejan, P A C., ten Brink, H., Phillips, G., Kortner, M., Meixner, F X., and Nemitz, E.: An automated analyzer to measure surface-atmosphere exchange fluxes of water soluble inorganic aerosol compounds and reactive trace gases, Environ. Sci. Technol., 43, 1412–1418, http://dx.doi.org/10.1021/es8019403doi:10.1021/es8019403, 2009.

Toon, O B., Pollack, J B., and Khare, B N.: Optical-Constants os Several Atmospheric Aerosol Species – Ammonium-Sulfate, Alluminum-Oxide, And Sodium-Chloride, J. Geophys. Res., 81, 5733–5748, http://dx.doi.org/10.1029/JC081i033p05733doi:10.1029/JC081i033p05733, 1976.

Troen, I B. and Mahrt, L.: A simple model of the atmospheric boundary layer; sensitivity to the surface evaporation, Bound. Lay. Meteorol., 37, 129–148, http://dx.doi.org/10.1007/BF00122760doi:10.1007/BF00122760, 1986.

Varutbangkul, V., Brechtel, F J., Bahrein, R., Ng, N L., Keywood, M D., Kroll, J H., Flagan, R C., Seinfeld, J H., Lee, A., and Goldstein, A H.: Hygroscopic of secondary organic aerosols formed by oxidation of cycloalkanes, monoterpenes, sesquiterpenes, and related compounds, Atmos. Chem. Phys., 6, 2367–2388, http://dx.doi.org/10.5194/acp-6-2367-2006doi:10.5194/acp-6-2367-2006, 2006.

Vestreng, V., Myhre, G., Fagerli, H., Reis, S., and Tarrasón, L.: Twenty-five years of continuous sulphur dioxide emission reduction in Europe, Atmos. Chem. Phys., 7, 3663–3681, http://dx.doi.org/10.5194/acp-7-3663-2007doi:10.5194/acp-7-3663-2007, 2007.

Vestreng, V., Ntziachristos, L., Semb, A., Reis, S. Isaksen, I S A., and Tarrasón, L.: Evolution of NO$_\mathrmx$ emissions in Europe with focus on road transport control measures, Atmos. Chem. Phys., 9, 1503–1520, http://dx.doi.org/10.5194/acp-9-1503-2009doi:10.5194/acp-9-1503-2009, 2009.

Vignati, E., Wilson, J., and Stier, P.: M7: An efficient size-resolved aerosol microphysics module for large-scale aerosol transport models, J. Geophys. Res., 109, D22202, http://dx.doi.org/10.1029/2003JD004485doi:10.1029/2003JD004485, 2004.

Wang, S C. and Flagan, R C.: Scanning electrical mobility spectrometer, Aerosol Sci. Technol., 13, 230–240, http://dx.doi.org/10.1080/02786829008959441doi:10.1080/02786829008959441, 1990.

Wang, J., Hoffmann, A A., Park, R J., Jacob, D J., and Martin, S T.: Global distribution of solid and aqueous sulfate aerosols: Effect of the hysteresis of particle phase transition, J. Geophys. Res., 103, D11206, http://dx.doi.org/10.1029/2007JD009367doi:10.1029/2007JD009367, 2008.

Weast, R C.: Handbook of Chemistry and Physics, 66th Edn., CRC Press, Florida, 1985.

Weijers, E P., Schaap, M., Nguyen, L., Matthijsen, J., Denier van der Gon, H A C., ten Brink, H M., and Hoogerbrugge, R.: Anthropogenic and natural constituents in particulate matter in the Netherlands, Atmos. Chem. Phys., 11, 2281–2294, http://dx.doi.org/10.5194/acp-11-2281-2011doi:10.5194/acp-11-2281-2011, 2011.

Wexler, A S. and Seinfeld, J H.: Analysis of aerosol ammonium nitrate departures from equilibrium during SCAQS, Atmos. Environ., 26A, 579–591, http://dx.doi.org/10.1016/0960-1686(92)90171-Gdoi:10.1016/0960-1686(92)90171-G, 1992.

Wiedensohler, A.: An approximation of the bipolar charge distribution for particles in the submicron size range, J. Aerosol Sci., 19, 387–389, http://dx.doi.org/10.1016/0021-8502(88)90278-9doi:10.1016/0021-8502(88)90278-9, 1988.

Yu, S., Dennis, R., Roselle, S., Nenes, A., Walker, J., Eder, B., Schere, K., Swall, J., and Robarge, W.: An assessment of the ability of three-dimensional air quality models with current thermodynamic equilibrium models to predict aerosol NO$_3^-$, J. Geophys. Res., 10, D07S13, 1–22, http://dx.doi.org/10.1029/2004JD004718doi:10.1029/2004JD004718, 2005.

Yu, X.-Y., Lee, T., Ayres, B., Kreidenweis, S M., Malm, W., and Collett, J. L J.: Loss of fine particulate ammonium from denuded nylon filters, Atmos. Environ., 40, 4797–4807, http://dx.doi.org/10.1016/j.atmosenv.2006.03.061doi:10.1016/j.atmosenv.2006.03.061, 2006.

Zhang, J., Charmeides, W L., Weber, R., Cass, G., Orsini, D., Edgerton, E., Jongejan, P., and Slanina, J.: An evaluation of the thermodynamic equilibrium assumption for fine particulate composition: Nitrate and ammonium during the 1999 Atlanta Supersite experiment, J. Geophys. Res., 108, 8414, http://dx.doi.org/10.1029/2001JD001592doi:10.1029/2001JD001592, 2003.

Zhang, X. and McMurry, P H.: Evaporative losses of fine particulate nitrates during sampling, Atmos. Environ., 26A, 3305–3312, http://dx.doi.org/10.1016/0960-1686(92)90347-Ndoi:10.1016/0960-1686(92)90347-N, 1992.